CN115367732A - Method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery in synergic manner - Google Patents
Method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery in synergic manner Download PDFInfo
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Abstract
The invention discloses a method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner, which comprises the steps of mixing waste nickel-cobalt-manganese-lithium battery anode powder, industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium battery cathode powder, then carrying out selective vulcanization roasting, recovering lithium from a vulcanization roasting product by adopting water leaching, recovering manganese from water leaching residues by adopting acid leaching, recovering nickel-cobalt sulfide from the acid leaching residues by flotation separation, or recovering nickel-cobalt sulfide from the water leaching residues by flotation separation, and recovering manganous oxide from flotation tailings by adopting magnetic separation. The method can utilize industrial sulfate solid wastes as resources, can simultaneously realize the high-efficiency recovery of nickel, cobalt, manganese, lithium and other elements in the lithium ion battery, and obtains raw materials for manufacturing a new nickel-cobalt-manganese-lithium battery.
Description
Technical Field
The invention relates to a solid waste treatment method, in particular to a synergic resource recycling method of industrial sulfate solid waste (sodium sulfate waste salt and/or industrial solid waste phosphogypsum) and waste nickel-cobalt-manganese-lithium batteries, and belongs to the technical field of solid waste resource recycling.
Background
With the rapid development of the global power automobile industry at present, the development of the lithium ion battery industry is full of vitality. The survey report released by the international energy agency in 2021 shows that the stock of the global power automobile is estimated to reach 4000 to 7000 thousands by 2025. The production of a large number of electric automobiles drives a large amount of consumption of lithium ion batteries, and green harmless treatment of waste lithium ion batteries is a new technical problem.
Although the lithium ion battery is called as a clean energy storage device, the retired waste lithium ion battery contains heavy metal elements such as nickel and cobalt, and the electrolyte, strong acid and strong alkaline electrolyte in the battery can pollute the environment. Compared with the traditional ore material, the grade of metal elements in the waste lithium ion battery is higher, such as 5-8 wt% of lithium, 15-48 wt% of nickel, 5-20 wt% of cobalt and 5-19 wt% of manganese. If the waste lithium ion battery electrode can be recycled in an environment-friendly and efficient manner, the problem of environmental pollution can be solved, and the external dependence of China on nickel, cobalt, manganese and lithium resources can be relieved.
A common lithium ion battery comprises lithium cobaltate (LiCoO) 2 ) Lithium manganate (LiMnO) 2 ) Lithium iron phosphate (LiFeO) 4 ) Lithium nickel cobalt manganese oxide (LiNi) x Co y Mn (1-x-y )O 2 ) And lithium manganese iron phosphate (LiMn) x Fe (1-x) PO 4), and the like. The type number, scale, batch and production technology of the lithium ion battery at present are different, the problems of slow recovery progress, high cost, large safety risk and the like exist in the recovery process, and a recovery process technology with simple process and low cost is urgently neededAnd (4) performing the operation.
The treatment of chemical waste salt is a big problem faced by China, and the traditional chemical industries of pesticide, coal chemical industry, petroleum, printing and dyeing textile and the like can bring a large amount of industrial waste salt which is difficult to treat, such as sodium chloride, sodium sulfate, sodium nitrate, potassium chloride and the like, during production. According to the data of the national statistical bureau, the annual output of industrial waste salt in China exceeds 2000 million tons, and single salt and mixed salt coexist. The traditional industrial waste salt treatment adopts rigid or wet landfill, the landfill treatment process is simple, the treatment capacity is large, the batch treatment of mixed waste salt can be realized, but the harmless treatment of the waste salt is required before the landfill. Taking the pesticide industry as an example, a great amount of toxic and harmful halogenated hydrocarbons and benzene organic compounds remain in the pesticide waste salt, and if the waste salt is directly buried, the buried land can be damaged. In addition to landfill treatment of industrial waste salt, the current industrial waste salt treatment process comprises a high-temperature pyrolysis method, a resin adsorption oxidation method, a salt washing method, a precipitation method and the like. The high-temperature pyrolysis removes residual organic matters by heating industrial waste salt. The process flow is simple, the industrial production is realized, but the production scale is limited by the defects of high energy consumption and high treatment cost. The resin adsorption and oxidation utilizes the porous adsorption characteristic of epoxy resin and is easy to desorb and regenerate, and the strong oxidizing property of hydroxyl free radicals is adopted in the oxidation process, so that the high-molecular degradation-resistant substances are decomposed into non-toxic and low-toxicity small-molecular compounds, and the high-efficiency treatment of industrial waste salt is realized. The epoxy resin oxidation adsorption method has simple process, low treatment cost and good product quality, is an effective means for treating industrial waste salt at present, but if elements such as phosphorus, calcium, magnesium and the like exist in the wastewater treated by the method, the wastewater can meet the discharge requirement by advanced treatment. The salt washing method and the precipitation method are both carried out in a solution system, and in actual production, a large amount of industrial wastewater is difficult to avoid, and secondary pollution is caused.
The phosphogypsum solid waste is industrial waste residue in the wet preparation of phosphoric acid, and the main component of the phosphogypsum solid waste is CaSO 4 ·2H 2 And O. According to global data it is shown that phosphogypsum is currently stockpiled in excess of 60 hundred million tons and is continuously rising at a rate of 1 hundred million tons per year. The stockpiling amount of the phosphogypsum in China exceeds 2.5 hundred million tons, most of the phosphogypsum is treated by landfill,the resource utilization degree is not high. Removal of CaSO from phosphogypsum 4 ·2H 2 Besides O, the phosphogypsum also contains phosphorus, fluorine compounds, heavy metals and organic matters, and direct landfill treatment can cause pollution sources to enter soil and underground water, so that the green resource utilization of the phosphogypsum is realized. At present, the comprehensive utilization of the phosphogypsum is mainly in the industries of agriculture, building industry and the like, but the comprehensive utilization of the phosphogypsum in China is still in the primary stage of the preparation of the cement retarder, the utilization efficiency is low, and the industrial solid waste phosphogypsum stockpiled up to now is difficult to consume.
Disclosure of Invention
The invention aims to provide a method for realizing resource recovery based on the cooperative treatment of industrial sulfate solid waste and waste anode and cathode powder of waste nickel cobalt lithium manganate batteries, which utilizes the industrial sulfate solid waste and waste nickel cobalt lithium manganate battery anode and cathode powder to carry out high-temperature solid-phase reaction, can realize the pyrolysis of organic matters in the industrial sulfate solid waste (sodium sulfate waste salt or phosphogypsum solid waste) and the like and the removal of low-boiling-point impurities by utilizing the high-temperature solid-phase reaction, simultaneously utilizes sulfate as a sulfur source to realize the selective vulcanization of nickel cobalt lithium manganate, converts lithium into water-soluble lithium salts and manganese into manganous oxide and nickel cobalt sulfide, and combines a low-cost green water leaching process to preferentially extract lithium, realizes the high-efficiency and low-cost separation and recovery of nickel cobalt manganese by utilizing a low-acid leaching or flotation separation process, can simultaneously recover nickel cobalt lithium ion batteries manufactured by different models, different manufacturers, can simultaneously realize the high-efficiency recovery of nickel, cobalt, manganese, lithium and the like elements in the lithium ion batteries, can be used for manufacturing new nickel cobalt lithium batteries, and the method is beneficial to large-scale industrial pollution of lithium ion batteries.
In order to realize the technical purpose, the invention provides a method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner, which comprises the following steps:
1) Mixing the waste nickel cobalt lithium manganate battery anode powder, industrial sulfate solid waste and waste nickel cobalt lithium manganate battery cathode powder, and then carrying out vulcanization roasting to obtain a vulcanization roasting product containing water-soluble lithium salt, nickel cobalt sulfide and manganous oxide;
2) Leaching the vulcanized and roasted product by water to recover lithium, wherein the water leaching slag contains nickel cobalt sulfide and manganous oxide;
3) Acid leaching is carried out on the water leaching slag to recover manganese, the acid leaching slag contains nickel cobalt sulfide, and the acid leaching slag is subjected to flotation separation to recover the nickel cobalt sulfide; or, separating the water leaching slag by flotation to recover nickel-cobalt sulfide, wherein flotation tailings contain manganous oxide, and recovering the manganous oxide from the flotation tailings by magnetic separation. Or; and separating the water leaching residue by flotation to recover nickel-cobalt sulfide, wherein flotation tailings contain manganous oxide, and acid leaching the flotation tailings to recover manganese.
The key point of the technical scheme is that the industrial sulfate solid wastes such as sodium sulfate waste salt, phosphogypsum solid wastes and the like and the anode and cathode powder of the waste nickel-cobalt-manganese-lithium battery are subjected to synergistic high-temperature roasting, for example, the sodium sulfate waste salt mainly contains sodium sulfate, organic pollutant halohydrocarbon, aromatic hydrocarbon, heterocyclic organic matter and trace heavy metal, the main components of the phosphogypsum solid wastes are calcium sulfate dihydrate and a small amount of phosphorus and fluorine impurities, in the high-temperature roasting process, the organic matter is fully pyrolyzed, the halide salt with low boiling point and the like are volatilized and removed, the sulfate is used as a sulfur source for the sulfuration roasting of the anode powder of the waste nickel-cobalt-manganese-lithium battery, and meanwhile, the salt components in the industrial sulfate solid wastes are also used as a fluxing agent to reduce the solid phase reaction temperature and promote the generation of a liquid phase, which is favorable for the growth of nickel-cobalt sulfide crystals, so as to obtain large metal sulfide particles which are easy to be separated by flotation. The nickel-cobalt-manganese-lithium battery cathode powder is very favorable for high-temperature solid-phase reaction, and the main component of the nickel-cobalt-manganese-lithium battery cathode powder is a carbon material, so that a sulfur source is prevented from being converted into sulfur dioxide gas to be volatilized in the vulcanizing and roasting process, the organic metal vulcanizing reaction can be promoted, the vulcanizing reaction temperature is reduced, and the selective vulcanizing efficiency is improved. Under the synergistic effect of the carbon material and the sulfur source, nickel and cobalt elements of the nickel-cobalt-manganese-lithium battery anode powder are converted into water-insoluble metal sulfides, manganese elements exist in a manganous oxide form (easy to leach by dilute acid or recover by magnetic separation), and lithium exists in a lithium salt form which is easy to dissolve in water, so that the subsequent separation and recovery of metal lithium, manganese, nickel and cobalt are facilitated.
As a preferable scheme, the mass ratio of the waste nickel cobalt lithium manganate battery cathode powder to the waste nickel cobalt lithium manganate battery cathode powder is 1-3.6. The matching proportion of the anode powder and the cathode powder of the waste nickel-cobalt lithium manganate battery is very important for selective vulcanization reaction, and the introduction of the carbon material can not only promote the high-efficiency transformation of the vulcanization reaction, but also reduce the content of sulfur dioxide gas converted from a sulfur source. The sulfur dioxide gas generated in the high-temperature process cannot be converted due to too low proportion of the cathode powder of the waste nickel cobalt lithium manganate battery, and the reduction of each metal element in the cathode material of the waste nickel cobalt lithium manganate battery is difficult to realize; too high proportion of the waste nickel cobalt lithium manganate battery cathode powder can cause metal phase in the roasted product, which is not beneficial to the separation of various metals in the follow-up process.
As a preferable scheme, the mass ratio of the total mass of the waste nickel-cobalt-manganese-lithium battery positive electrode powder and the waste nickel-cobalt-manganese-lithium battery negative electrode powder to the industrial sulfate solid waste is 3 to 1. The use amount of industrial sulfate solid waste is controlled in a proper range, and the complete vulcanization of nickel cobalt metal is favorably realized. If the solid-to-waste ratio of the industrial sulfate is too low, the nickel and cobalt are not completely vulcanized, and the subsequent recovery efficiency is reduced; if the solid-to-waste ratio of the industrial sulfate is too high, partial manganese vulcanization is easily caused, and the purpose of selectively vulcanizing nickel and cobalt is difficult to achieve.
As a preferred solution, the industrial sulfate solid waste comprises sodium sulfate waste salt and/or phosphogypsum. The sodium sulfate waste salt is derived from wastewater treated by petrochemical industry, coal chemical industry and waste batteries, and mainly comprises sodium sulfate, a small amount of organic pollutants such as halogenated hydrocarbons, aromatic hydrocarbons, heterocyclic organic matters and trace heavy metals. The industrial solid waste phosphogypsum is a byproduct for producing phosphoric acid, and mainly contains calcium sulfate dihydrate containing a small amount of phosphorus and fluorine impurities.
As a preferred scheme, the conditions of the sulfurizing roasting are as follows: the atmosphere is nitrogen and/or inert gas, the temperature is 700-1000 ℃, and the time is 60-180 min. In an optimal vulcanization roasting temperature range, the efficient selective vulcanization of nickel and cobalt in the waste nickel-cobalt-manganese-lithium battery anode powder can be ensured, and the metal crystalline phase and the grain size can be adjusted through roasting temperature and time, so that the flotation separation of nickel-cobalt sulfide is favorably realized. The roasting temperature is lower than the optimal range, so that the molding of each metal crystalline phase cannot be realized, and the subsequent phase separation is hindered; the sulfur source can be dissipated due to overhigh roasting temperature, and the selective vulcanization of the waste nickel-cobalt-manganese-lithium anode material can not be controlled.
As a preferable scheme, the water immersion conditions are as follows: the water immersion temperature is 30-95 ℃; the solid-liquid ratio is 50-150 g/L, and the leaching time is 30-300 min. After sulfuration roasting, the lithium salt mainly exists in the forms of sulfate with good water solubility and the like, and is easy to be leached by water to realize separation and recovery. And then carbonating and precipitating to obtain a high-purity lithium carbonate product.
As a preferred embodiment, the acid leaching conditions are as follows: the acid leaching temperature is 40-95 ℃, the solid-to-liquid ratio is 50-200 g/L, the leaching time is 30-360 min, and the acid is sulfuric acid with the concentration of 0.5-3 mol/L. After sulfuration roasting, manganese mainly exists in the form of manganous oxide, and is easy to leach by dilute sulfuric acid to realize separation and recovery.
In a preferable mode, the magnetic field intensity for the magnetic separation is 50 to 300mT. The manganous oxide with magnetism can be efficiently separated by proper magnetic field intensity.
In a preferable scheme, xanthate and/or blackant is used as a collecting agent, pine oil is used as a foaming agent, at least one of water glass, sodium humate and water-soluble starch is used as an inhibitor, and sodium hydroxide and/or sodium carbonate is used as a pH regulator in the flotation separation process. As a preferable scheme, the dosage of the collecting agent relative to acid leaching slag is 200-600 g/t; the dosage of the inhibitor relative to acid leaching residue is 50-200 g/t; the dosage of the foaming agent relative to the acid leaching residue is 20-100 g/t. After the sulfuration roasting, nickel and cobalt mainly exist in a nickel and cobalt sulfide form, have large particles, and are easy to obtain high-efficiency enrichment by adopting a common metal sulfide flotation separation method.
The lithium recovered by water leaching can be purified, purified and converted by carbonation to obtain high-purity lithium carbonate precipitate.
According to the method, pure manganese sulfate is obtained by removing impurities from manganese recovered by acid leaching, or manganous oxide is recovered in a magnetic separation mode.
The method adopts the nickel-cobalt sulfide separated by flotation to directly calcine the nickel-cobalt sulfide with a lithium source and a manganese source to obtain the nickel-cobalt-manganese lithium.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1) According to the method, the industrial sulfate solid waste is utilized to selectively vulcanize the anode powder and the cathode powder of the waste nickel-cobalt-manganese-lithium battery, so that not only are the sulfur source in the industrial sulfate solid waste and the carbon source in the cathode powder of the waste nickel-cobalt-manganese-lithium battery fully utilized, but also the oriented vulcanization conversion and the separation recovery of valuable metals in the cathode powder of the waste nickel-cobalt-manganese-lithium battery are realized, and the synergic resource treatment and utilization of the anode powder and the cathode powder of the waste nickel-cobalt-manganese-lithium battery and organic pollution waste salt are really realized.
2) The method is based on the selective vulcanization of valuable metals in the positive electrode powder of the waste nickel-cobalt-manganese-lithium battery, so that the solubility difference of nickel-cobalt-manganese and lithium which are difficult to separate is increased, and the water immersion preferential extraction, dilute acid extraction or magnetic separation recovery of manganese and the flotation separation and enrichment of nickel-cobalt sulfide are realized.
3) The invention utilizes the industrial sulfate solid waste as the fluxing agent in the process of sulfuration roasting, can reduce the melting point of the system, promote the grain growth and the perfect crystallization of the nickel cobalt sulfide, is beneficial to the subsequent flotation separation, and can realize the deep degradation of organic pollutants and the volatilization removal of low-boiling-point impurities in the industrial sulfate solid waste in the process of high-temperature roasting.
4) The invention simultaneously utilizes the nickel-cobalt-manganese-lithium battery cathode powder, the introduction of the cathode powder is very favorable for high-temperature solid-phase reaction, and the main component of the nickel-cobalt-manganese-lithium battery cathode powder is a carbon material, so that the sulfur source is prevented from being converted into sulfur dioxide gas to be volatilized in the process of vulcanizing roasting, the organic metal vulcanization reaction can be promoted, the vulcanization reaction temperature is reduced, and the selective vulcanization efficiency is improved.
5) The method utilizes the sulfate in the industrial sulfate solid waste to carry out vulcanization roasting treatment on the waste nickel-cobalt-manganese-lithium battery, obtains battery-grade raw materials of lithium carbonate, manganese sulfate (or manganous oxide), nickel sulfide and cobalt sulfide, and simultaneously consumes a large amount of industrial sulfate solid waste.
Drawings
FIG. 1 is a process flow diagram of example 1.
FIG. 2 is a process flow diagram of example 4.
FIG. 3 is an XRD physical phase diagram of a product obtained by selective sulfidation roasting of the anode powder of the waste nickel cobalt lithium manganate battery in example 1; through selective vulcanization roasting, the selective vulcanization of the anode material of the waste nickel-cobalt-manganese-lithium battery is realized, lithium is converted into soluble lithium carbonate, nickel and cobalt are sulfides, and manganese is an oxide (manganous oxide), so that the subsequent acid leaching and flotation separation processes are facilitated.
Fig. 4 is an XRD physical phase diagram of a product obtained by selective sulfidation roasting of the anode powder of the waste nickel cobalt lithium manganate battery in comparative example 1, and because the addition proportion of the cathode powder of the waste nickel cobalt lithium manganate battery is too small, the reduction of manganese element is incomplete, and high-valence manganese exists, which affects the subsequent leaching or flotation process.
FIG. 5 is an XRD physical phase diagram of the product of selective sulfidation roasting of the anode powder of the waste nickel cobalt lithium manganate battery in comparative example 2; because the temperature of the selective sulfurizing roasting is higher, the sulfur source escapes, and cobalt-nickel oxysulfide exists in the sulfurizing roasting product to influence the floatation process.
FIG. 6 is an SEM-EDS diagram of the product of selective sulfidation roasting of the positive electrode powder of the waste nickel cobalt lithium manganate battery in example 1; the energy spectrum analysis of the vulcanized and roasted product finds that the point A is cobalt sulfide, the point B is nickel sulfide, the light color area of the point C is nickel-cobalt alloy, and the dark color area of the point D is manganese oxide; and a literal structure generated by the decomposition of a solid solution of nickel-cobalt sulfide through high-temperature mutual dissolution and cooling in the roasting process appears above the point B, and further proves that the selective roasting only vulcanizes the nickel and cobalt in the anode material of the waste nickel-cobalt-manganese-lithium battery.
Detailed Description
The following specific examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Mixing the anode powder and the cathode powder of the waste nickel-cobalt-manganese-lithium battery according to a ratio of 3, then fully mixing the mixed electrode powder of the waste lithium ion battery with sodium sulfate waste salt (the main components of sodium sulfate account for 85%, organic pollutant halogenated hydrocarbon, aromatic hydrocarbon and heterocyclic organic matter account for 10%, trace heavy metal accounts for 1% and the like) according to a mass ratio of 3. And (3) converting rare and precious metal phases in the waste nickel-cobalt-manganese-lithium battery through vulcanization roasting. Leaching the obtained roasting product for 120min at room temperature according to 1g of liquid-solid ratio 9mL, wherein the leaching rate of lithium reaches 95.07%, and lithium sulfate is converted into lithium carbonate through carbonation; leaching the water leaching slag by sulfuric acid, wherein the concentration of sulfuric acid is 2mol/L, the liquid-solid ratio is 10mL, the leaching temperature is 85 ℃, the leaching time is 90min, obtaining nickel-cobalt sulfide leaching slag and a manganese sulfate solution, and purifying and separating the manganese sulfate solution to obtain high-purity manganese sulfate, wherein the leaching rate of manganese is 97.21%.
Grinding the nickel and cobalt leaching slag until the grain size of-0.074 mm accounts for 90.12%, setting a flotation machine to operate at 800r/min for 15min and adjusting the concentration of ore pulp to 20%; adding collecting agent xanthate (the addition amount of the xanthate to raw ore is 500 g/t) into the ore pulp, stirring for 10min, and adding foaming agent terpineol (the addition amount of the terpineol to raw ore is 20 g/t) and pH regulator sodium hydroxide to control the pH of the ore pulp to be 7. And performing flotation and foam scraping operation, wherein the process lasts for 10min. The obtained concentrate product is purified and separated to obtain nickel-cobalt sulfide, wherein the recovery rates of nickel and cobalt are 95.69% and 94.96% respectively. The high-purity lithium carbonate, manganese sulfate and nickel cobalt sulfide obtained by the experiment can be used for preparing the nickel cobalt manganese lithium battery by a subsequent means.
Example 2
Mixing anode and cathode powders of a waste nickel-cobalt-manganese-lithium battery according to a ratio of 5.4, adding sodium sulfate waste salt (main components including 86% of sodium sulfate, organic pollutant halohydrocarbon, aromatic hydrocarbon and heterocyclic organic matter, 1% of trace heavy metal and the like) into the mixed anode and cathode powders according to a mass ratio of 1. And drying the filtered leaching residue, and performing secondary leaching by using sulfuric acid. And (3) obtaining a manganese sulfate solution and nickel cobalt sulfide leaching residues in the leaching process, wherein the sulfuric acid concentration is 2mol/L, the liquid-solid ratio is 15mL, the leaching temperature is 90 ℃, the leaching time is 180min, and the leachate is separated and purified to obtain high-purity manganese sulfate, and the manganese leaching rate is 97.74%.
Grinding the sulfuric acid leaching slag until the size fraction of-0.074 mm accounts for 94.21%, setting the rotation speed of a flotation agent to be 900r/min, operating for 20min, and adjusting the concentration of ore pulp to be 30%; adding a collector xanthate (the addition amount of the xanthate relative to the raw ore is 600 g/t) into the ore pulp, stirring for 15min, adding a foaming agent, namely pine oil (the addition amount of the pine oil relative to the raw ore is 30 g/t) and a pH regulator, namely sodium hydroxide, to control the pH of the ore pulp to be 7, and then carrying out flotation and foam scraping for 20min to obtain a roughed product. The primary concentrate is the nickel cobalt sulfide which is purified and separated, wherein the recovery rates of the nickel cobalt are 94.53 percent and 92.97 percent respectively. The high-purity nickel-cobalt sulfide can be supplemented with manganese and lithium by a subsequent means to prepare the nickel-cobalt-manganese-lithium battery.
Comparative example 1
Mixing anode powder and cathode powder of the waste nickel-cobalt-manganese-lithium battery according to the mass ratio of 5 to 1, mixing the mixed anode powder with sodium sulfate waste salt (the main components of sodium sulfate account for 85%, organic pollutant halohydrocarbon, aromatic hydrocarbon and heterocyclic organic matter account for 10%, trace heavy metal accounts for 1% and the like) in a mass ratio of 3. The result shows that the selective sulfurizing roasting obtains manganese oxides with different valence states, and the high-valence state manganese is not beneficial to subsequent acid leaching and separation and purification of manganese. In order to ensure the efficient recovery of manganese, the proportion of the cathode powder of the waste nickel-cobalt-manganese-lithium battery is increased, and the full reduction of nickel-cobalt-manganese elements is ensured.
Comparative example 2
Mixing anode powder and cathode powder of the waste nickel-cobalt-manganese-lithium battery according to the mass ratio of 3 to 1, mixing the mixed anode powder with sodium sulfate waste salt (the main components of sodium sulfate account for 85%, organic pollutant halohydrocarbon, aromatic hydrocarbon and heterocyclic organic matter account for 10%, trace heavy metal accounts for 1% and the like) according to the mass ratio of 3 to 2, placing the mixed sample in a tubular furnace, roasting the sample at 1200 ℃ for 120min in a nitrogen atmosphere, and detecting the sample by XRD to obtain the result shown in figure 5. Because of the over-high roasting, the sulfur source is dissipated, the nickel cobalt sulfide and the oxide thereof are obtained, and the nickel cobalt metal is incompletely selected and vulcanized. In order to ensure the selective vulcanization of the anode material of the waste nickel-cobalt-manganese-lithium battery, the roasting temperature should be controlled in a preferred scheme interval, so as to reduce the loss of a sulfur source.
Comparative example 3
Mixing the anode powder and the cathode powder of the waste nickel-cobalt-lithium-manganese battery according to the proportion of 3. And (3) after the roasted product is ground, leaching for 90min at room temperature according to the liquid-solid ratio of 9 mL. Filtering and drying the product, grinding until the grain size of minus 0.074mm accounts for 91.87%, setting the rotation speed of the flotation agent to be 800r/min, operating for 15min, and adjusting the concentration of ore pulp to be 20%; adding collecting agent xanthate (the addition amount of which is 500g/t relative to the raw ore) into the ore pulp, stirring for 10min, adding foaming agent terpineol (the addition amount of which is 20g/t relative to the raw ore) and pH regulator sodium hydroxide to control the concentration of the ore pulp to be 7, and then carrying out foam scraping for 10min to obtain a roughing product. The primary concentrate is a purified and separated nickel-cobalt-manganese sulfide, wherein the recovery rates of nickel, cobalt and manganese are respectively 93.87%, 93.61% and 95.62%, nickel, cobalt and manganese are selected together, and selective vulcanization of nickel and cobalt in the waste lithium battery cannot be realized.
Example 3
Mixing the anode powder and the cathode powder of the waste nickel-cobalt-manganese-lithium battery according to the proportion of 2 4 ·2H 2 91.92% of O and P 2 O 5 2.38% and 0.59% of F) according to the mass ratio of 3 to 2, placing the mixed sample into a tubular furnace, carrying out vulcanization roasting at 900 ℃ for 120min, grinding the roasted product, leaching the product at room temperature for 150min according to a liquid-solid ratio of 10mL. Grinding the leached slag until the grain size of-0.074 mm accounts for 92.84%, setting a flotation machine to operate at 900r/min for 15min and adjusting the concentration of ore pulp to 20%; adding collector xanthate (the addition amount of which relative to the crude ore is 600 g/t) into the ore pulp, stirring for 15min, and adding foaming agent terpineol (the addition amount of which relative to the crude ore is 20 g/t) and pH regulator sodium hydroxide to control the pH of the ore pulp to be 7. And (5) carrying out flotation and foam scraping operation, wherein the process lasts for 5min. The obtained concentrate product is purified and separated to obtain nickel-cobalt sulfide, wherein the recovery rates of nickel and cobalt are 95.34% and 94.02% respectively. Leaching the flotation tailings by using sulfuric acid, wherein the concentration of the sulfuric acid is 1.5mol/L, the liquid-solid ratio is 1g, the leaching temperature is 90 ℃, the leaching time is 120min, nickel-cobalt sulfide leaching residues and a manganese-containing solution are obtained, and the manganese-containing solution is purified and separated to obtain high-purity manganese sulfate, and the leaching rate of the manganese is 97.64%. The battery-grade lithium carbonate, manganese sulfate and nickel cobalt sulfide obtained by the experiment can be used for preparing the nickel cobalt manganese lithium battery by a subsequent means.
Example 4
Mixing anode and cathode powders of the waste nickel-cobalt-manganese-lithium battery according to the proportion of 2 4 ·2H 2 91.92% of O and P 2 O 5 2.38 percent and 0.59 percent of F), placing the mixed sample into a tube furnace, heating to 900 ℃ in a nitrogen atmosphere, preserving the heat for 120min, leaching the roasted product for 90min at room temperature according to the liquid-solid ratio of 10mL. Drying the leached slag after filtrationGrinding until the grain size of-0.074 mm accounts for 90.32%, setting the rotation speed of a flotation agent to 900r/min, running for 20min, and adjusting the concentration of ore pulp to 30%; adding a collector xanthate (the addition amount of the xanthate relative to the raw ore is 600 g/t) into the ore pulp, stirring for 15min, adding a foaming agent, namely pine oil (the addition amount of the pine oil relative to the raw ore is 30 g/t) and a pH regulator, namely sodium hydroxide, to control the pH of the ore pulp to be 7, and then carrying out flotation and foam scraping for 20min to obtain a roughed product. The primary concentrate is the nickel cobalt sulfide which is purified and separated, wherein the recovery rates of the nickel cobalt are 94.53 percent and 92.97 percent respectively. And (3) separating and purifying the roughed tailings by magnetic separation, wherein the magnetic field intensity of a used magnetic separator is 300Mt, the roller rotating speed is 50rpm, and the final manganese recovery rate is 97.62%. The lithium sulfate solution, the high-purity nickel-cobalt sulfide and the manganese oxide of the experiment can be used for preparing the nickel-cobalt-manganese-lithium battery by subsequent means.
Comparative example 4
Fully and uniformly mixing the anode powder and the cathode powder of the waste nickel-cobalt-manganese-lithium battery according to the mass ratio of 2 to 1, and adding industrial phosphogypsum (the main component is CaSO) into the mixed battery anode powder according to the mass ratio of 1 4 ·2H 2 91.92% of O and P 2 O 5 Accounting for 2.38 percent and F content of 0.59 percent), mixing, heating the mixed sample to 900 ℃ in a tube furnace under the protection of nitrogen, preserving heat for 120min, and soaking a roasted product in 1 mL of water at room temperature for 150min according to a liquid-solid ratio of 10mL, wherein the lithium leaching rate reaches 94.59 percent. Drying the filter residue, and grinding to a particle size fraction of-0.074 mm which accounts for 90.46%. Setting the rotation speed of a flotation machine to be 900r/min, operating for 15min, adjusting the concentration of ore pulp to be 20%, adding a collecting agent xanthate (the addition amount of the xanthate relative to the raw ore is 600 g/t), stirring for 15min, adding a foaming agent terpineol (the addition amount of the terpineol relative to the raw ore is 20 g/t) and a pH adjusting agent sodium hydroxide to control the pH of the ore pulp to be 7, and carrying out flotation and foam scraping for 15min to obtain a roughed product. The primary concentrate is the purified and separated nickel-cobalt-manganese sulfide, and the recovery rates of nickel, cobalt and manganese are respectively 94.53%, 92.97% and 95.62%. Because of adding excessive sulfur source, the nickel, cobalt and manganese elements are completely vulcanized, and the aim of selectively vulcanizing the elements of the anode material of the waste lithium ion battery cannot be realized.
Claims (10)
1. A method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner is characterized by comprising the following steps: the method comprises the following steps:
1) Mixing the waste nickel cobalt lithium manganate battery anode powder, industrial sulfate solid waste and waste nickel cobalt lithium manganate battery cathode powder, and then carrying out vulcanization roasting to obtain a vulcanization roasting product containing water-soluble lithium salt, nickel cobalt sulfide and manganous oxide;
2) Leaching the vulcanized and roasted product by water to recover lithium, wherein the water leaching slag contains nickel cobalt sulfide and manganous oxide;
3) Acid leaching is carried out on the water leaching slag to recover manganese, the acid leaching slag contains nickel cobalt sulfide, and the acid leaching slag is subjected to flotation separation to recover the nickel cobalt sulfide; or, separating the water leaching slag by flotation to recover nickel-cobalt sulfide, wherein flotation tailings contain manganous oxide, and recovering the manganous oxide from the flotation tailings by magnetic separation; or, separating the water leaching slag by flotation to recover nickel cobalt sulfide, wherein flotation tailings contain manganous oxide, and acid leaching the flotation tailings to recover manganese.
2. The method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner according to claim 1, characterized in that: the mass ratio of the total mass of the waste nickel cobalt manganese lithium battery anode powder and the waste nickel cobalt manganese lithium battery cathode powder to the industrial sulfate solid waste is (3).
3. The method for recycling industrial sulfate solid waste and waste nickel cobalt manganese lithium batteries according to claim 2, is characterized in that: the mass ratio of the waste nickel cobalt lithium manganate battery cathode powder to the waste nickel cobalt lithium manganate battery cathode powder is (1-3.6).
4. The cooperative recycling method for sodium sulfate waste salt and waste nickel-cobalt-manganese-lithium batteries according to any one of claims 1 to 3, characterized in that: the industrial sulfate solid waste comprises sodium sulfate waste salt and/or phosphogypsum.
5. The method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner according to claim 4, wherein:
the main component of the waste sodium sulfate salt is sodium sulfate, and the waste sodium sulfate salt also contains organic pollutants such as halogenated hydrocarbon, aromatic hydrocarbon, heterocyclic organic matters and trace heavy metals;
the main component of the phosphogypsum is calcium sulfate dihydrate, and a small amount of phosphorus and fluorine impurities are also contained.
6. The method for the cooperative recycling of industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries according to claim 1, characterized by comprising the following steps: the conditions of the sulfuration roasting are as follows: the atmosphere is nitrogen and/or inert gas, the temperature is 700-1000 ℃, and the time is 60-180 min.
7. The method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner according to claim 1, characterized in that: the water leaching conditions are as follows: the water immersion temperature is 30-95 ℃; the solid-liquid ratio is 50-150 g/L, and the leaching time is 30-300 min.
8. The method for the cooperative recycling of industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries according to claim 1, characterized by comprising the following steps: the acid leaching conditions are as follows: the acid leaching temperature is 40-95 ℃, the solid-to-liquid ratio is 50-200 g/L, the leaching time is 30-360 min, and the acid is sulfuric acid with the concentration of 0.5-3 mol/L.
9. The method for the cooperative recycling of industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries according to claim 1, characterized by comprising the following steps:
in the flotation separation process, xanthate and/or nigre are used as collecting agents, pine oil is used as a foaming agent, at least one of water glass, sodium humate and water-soluble starch is used as an inhibitor, and sodium hydroxide and/or sodium carbonate is used as a pH regulator;
the magnetic field intensity adopted by the magnetic separation is 50-300 mT.
10. The method for recycling industrial sulfate solid waste and waste nickel-cobalt-manganese-lithium batteries in a synergic manner according to claim 9, wherein:
the dosage of the collecting agent relative to the acid leaching residue is 200-600 g/t;
the dosage of the inhibitor relative to acid leaching residue is 50-200 g/t;
the dosage of the foaming agent relative to the acid leaching residue is 20-100 g/t.
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